Electrochemical catalyst and preparation method therefor

ABSTRACT

Provided are an electrochemical catalyst and a preparation method therefor. The preparation method for an electrochemical catalyst may comprise the steps of preparing a base metal aqueous solution containing a base metal, hydrothermally synthesizing a base structure containing an oxide of the base metal by using the base metal aqueous solution, and using a heat treatment method for the base structure in a sulfur (S)-containing reactive gas atmosphere, exchanging oxygen (O) on the surface of the base structure with sulfur (S) of the reactive gas to form a catalyst structure which has a core structure containing the oxide of the base metal and a shell structure containing a sulfide of the base metal.

TECHNICAL FIELD

The present invention relates to an electrochemical catalyst and a method for preparing the same, and more particularly, to an electrochemical catalyst having a metal oxide and a metal sulfide and a method for preparing the same.

BACKGROUND ART

So far, the world's energy has been heavily dependent on energy sources such as coal, crude oil, natural gas, etc. Fossil fuels, nonrenewable energy which relies on limited sources that diminish with use, are either too expensive or cause a lot of damage to the environment. Thus, the creation of clean energy is required for the survival, health, and affluent life of human beings in the future of the 21st century.

One of the key technologies most needed to achieve clean energy is energy conversion, energy production, and energy storage using electrocatalysts. Typically, solar cells, batteries, fuel cells, hydrogen/oxygen/hydrocarbon generators, and electrochromic devices belong to applications closely related to electrochemical catalysts and are technologies using the principle of electrochemical catalysts. Accordingly, countries around the world are sparing no effort, time, and investment to preempt the source technology of electrochemical catalysts.

In particular, the development of low-cost and high-efficiency energy conversion systems is an important area that can provide solutions to future energy problems, and the core part of these energy conversion devices is electrochemical catalysts. Currently, it is expensive noble metal catalysts that are most commonly used. However, since precious metal catalysts have limited reserves and require high costs, studies have been continuously conducted on electrochemical catalysts without using noble metals.

DISCLOSURE Technical Problem

One technical object of the present invention is to provide an electrochemical catalyst applicable to an oxygen evolution reaction (OER) or a hydrogen evolution reaction (HER), and a method for preparing the same.

Another technical object of the present invention is to provide an electrochemical catalyst with improved efficiency of oxygen evolution reaction (OER), and a method for preparing the same.

Still, another technical object of the present invention is to provide an electrochemical catalyst with improved efficiency of hydrogen evolution reaction (HER), and a method for preparing the same.

Still, another technical object of the present invention is to provide an electrochemical catalyst, which may be prepared through a top-down synthesis, and a method for preparing the same.

Still, another technical object of the present invention is to provide an electrochemical catalyst with a simplified process, and a method for preparing the same.

Still, another technical object of the present invention is to provide an electrochemical catalyst, to which a large-scale process is easily applied, and a method for preparing the same.

The technical objects of the present invention are not limited to the above.

Technical Solution

To solve the above technical objects, the present invention may provide a method for preparing an electrochemical catalyst.

According to one embodiment, the method for preparing an electrochemical catalyst may include the steps of providing a base metal aqueous solution containing a base metal, hydrothermally synthesizing a base structure containing an oxide of the base metal by using the base metal aqueous solution, and using a heat treatment method for the base structure in a sulfur (S)-containing reaction gas atmosphere, exchanging oxygen (O) on a surface of the base structure with the sulfur (S) of the reaction gas to form a catalyst structure which has a core structure containing the oxide of the base metal and a shell structure containing a sulfide of the base metal.

According to one embodiment, the reaction gas may include hydrogen sulfide (H₂S), and the hydrogen sulfide may be decomposed into sulfur (S) and hydrogen (H), in the forming of the catalyst structure, in which the decomposed sulfur (S) may be adsorbed on the surface of the base structure, and the decomposed hydrogen (H) may penetrate an inside of the base structure.

According to one embodiment, a plurality of pores may be formed in the base structure as the decomposed hydrogen (H) may penetrate inside of the base structure and react with the oxide of the base metal.

According to one embodiment, the base structure heat-treated in the reaction gas atmosphere may include a first base metal oxide, and a second base metal oxide in which the first base metal oxide may react with hydrogen (H) penetrated the inside of the base structure.

According to one embodiment, the shell structure may include a first base metal sulfide in which the oxygen (O) on the surface of the base structure is exchanged with the sulfur (S) of the reaction gas and a second base metal sulfide in which the first base metal sulfide is decomposed.

According to one embodiment, the providing of the base metal aqueous solution may include: preparing a source solution in which cobalt(II) nitrate hexahydrate is mixed with a solvent and mixing the source solution with polyvinylpyrrolidone.

To solve the above technical objects, the present invention may provide an electrochemical catalyst.

According to one embodiment, the electrochemical catalyst may include: a core structure including a first cobalt oxide, and a second cobalt oxide having a composition ratio different from that of the first cobalt oxide; and a shell formed on a surface of the core structure and including a first cobalt sulfide, and a second cobalt sulfide having a composition ratio different from that of the first cobalt sulfide, in which a content of the first cobalt oxide, the second cobalt oxide, the first cobalt sulfide, and the second cobalt sulfide may be controlled to improve oxygen generation efficiency in an oxygen evolution reaction (OER).

According to one embodiment, the first and second cobalt oxides may include Co₃O and CoO, respectively, and the first and second cobalt sulfides may include Co₃S₄ and CoS, respectively.

According to one embodiment, the electrochemical catalyst may include 49 wt % or more of the first cobalt oxide, 40 wt % or less of the second cobalt oxide, 11 wt % or less of the first cobalt sulfide, and 0.5 wt % or less of the second cobalt sulfide. According to one embodiment, the core structure may have a porous structure.

According to one embodiment, the diameter of pores formed in the core structure may be 12 nm or less.

According to another embodiment, the electrochemical catalyst may include a base structure in a form of a flat plate including a metal; a first material layer formed on a surface of the base structure and including an oxide of the metal; and a second material layer formed on a surface of the first material layer and including a sulfide of the metal.

According to another embodiment, the metal may include any one of cobalt (Co), molybdenum (Mo), tungsten (W), or vanadium (V).

According to another embodiment, the electrochemical catalyst may be used as a catalyst for an oxygen evolution reaction (OER) or a hydrogen evolution reaction (HER).

Advantageous Effects

A catalyst structure according to an embodiment of the present invention can include a core structure having a porous structure, and a shell structure formed on a surface of the core structure, in which the core structure can include a first base metal oxide (e.g., Co₃O₄) and a second base metal oxide (e.g., CoO), and the shell structure can include a first base metal sulfide (e.g., Co₃O₄) and a second base metal sulfide (e.g., CoS). Accordingly, the catalyst structure can be used as a catalyst for an oxygen evolution reaction (OER), thereby improving oxygen generation efficiency.

In addition, in the method for preparing an electrochemical catalyst according to an embodiment of the present invention, hydrogen sulfide (H₂S) having high reducing power can be used in the process of preparing the catalyst structure, and thus a top-down synthesis method starting from bulk particles can be applied. Accordingly, the preparation process can be simplified and a method for preparing an electrochemical catalyst suitable for a large-scale production process can be provided.

DESCRIPTION OF DRAWINGS

FIG. 1 is a flowchart explaining a method for preparing an electrochemical catalyst according to the first embodiment of the present invention.

FIG. 2 is a view showing a process of preparing an electrochemical catalyst according to a second embodiment of the present invention.

FIG. 3 is a view showing SEM images of a catalyst structure and a base structure according to Example 1 of the present invention.

FIG. 4 is a view showing TEM images of a catalyst structure and a base structure according to Example 1 of the present invention.

FIG. 5 is a view showing TEM images and EDS mapping images of a catalyst structure according to Example 1 of the present invention.

FIG. 6 is a view showing the results of XRD analysis of a catalyst structure and a base structure according to Example 1 of the present invention.

FIG. 7 is a graph showing an area of a catalyst structure and a base structure according to Example 1 of the present invention.

FIGS. 8 to 10 are views showing results of XPS analysis of a catalyst structure and a base structure according to Example 1 of the present invention.

FIG. 11 is a view showing the electrochemical properties of a catalyst structure and a base structure according to Example 1 of the present invention.

FIGS. 12 to 15 are graphs showing electrochemically active surface areas of a catalyst structure and a base structure according to Example 1 of the present invention.

FIG. 16 is a graph showing the stability of a catalyst structure according to Example 1 of the present invention.

FIG. 17 is a view showing FE-SEM images of a catalyst structure and a base structure according to Example 2 of the present invention.

FIG. 18 is a view showing TEM images of a catalyst structure and a base structure according to Example 2 of the present invention.

FIG. 19 is a view showing EDS mapping images of a catalyst structure according to Example 2 of the present invention.

FIG. 20 is a view showing the results of XRD analysis of a catalyst structure and a base structure according to Example 2 of the present invention.

FIG. 21 is a view showing an area of a catalyst structure and a base structure according to Example 2 of the present invention.

FIGS. 22 to 24 are views showing electrochemical properties of a catalyst structure and a base structure according to Example 2 of the present invention.

FIG. 25 is a graph showing electrochemically active surface areas and stability of a catalyst structure and a base structure according to Example 2 of the present invention.

FIG. 26 is a view showing FE-SEM images of a base structure according to Example 3 of the present invention.

FIG. 27 is a view showing FE-SEM images of a catalyst structure according to Example 3 of the present invention.

FIG. 28 is a view showing TEM images of a catalyst structure and a base structure according to Example 3 of the present invention.

FIG. 29 is a view showing the results of XRD analysis of a catalyst structure and a base structure according to Example 3 of the present invention.

FIG. 30 is a view showing an area of a catalyst structure and a base structure according to Example 3 of the present invention.

FIGS. 31 to 33 are views showing electrochemical properties of a catalyst structure and a base structure according to Example 3 of the present invention.

FIG. 34 is a graph showing electrochemically active surface areas and stability of a catalyst structure and a base structure according to Example 2 of the present invention.

FIG. 35 is a view showing FE-SEM images of a base structure according to Example 4 of the present invention.

FIG. 36 is a view showing FE-SEM images of a catalyst structure according to Example 4 of the present invention.

FIG. 37 is a view showing results of XRD analysis of a catalyst structure and a base structure according to Example 4 of the present invention.

FIG. 38 is a view showing an area of a catalyst structure and a base structure according to Example 4 of the present invention.

FIG. 39 is a view showing electrochemical properties of a catalyst structure and a base structure according to Example 4 of the present invention.

MODE FOR INVENTION

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the technical idea of the present invention is not limited to the embodiments described herein and may be embodied in other forms. The embodiments introduced herein are provided to sufficiently deliver the spirit of the present invention to those skilled in the art so that the disclosed contents may become thorough and complete.

When it is mentioned in the specification that one element is on another element, it means that the first element may be directly formed on the second element or a third element may be interposed between the first element and the second element. Further, in the drawings, the thicknesses of membranes and areas are exaggerated for efficient description of the technical contents.

Further, in the various embodiments of the present specification, the terms such as first, second, and third are used to describe various elements, but the elements are not limited to the terms. The terms are used only to distinguish one element from another element. Accordingly, an element mentioned as the first element in one embodiment may be mentioned as the second element in another embodiment. The embodiments illustrated here include their complementary embodiments. Further, the term “and/or” in the specification is used to include at least one of the elements enumerated in the specification.

In the specification, the terms of a singular form may include plural forms unless otherwise specified. Further, the terms “including” and “having” are used to designate that the features, the numbers, the steps, the elements, or combinations thereof described in the specification are present, and are not to be understood as excluding the possibility that one or more other features, numbers, steps, elements, or combinations thereof may be present or added. In addition, the term “connection” used herein may include the meaning of indirectly connecting a plurality of components, and directly connecting a plurality of components.

Further, in the following description of the present invention, a detailed description of known functions or configurations incorporated herein will be omitted when it may make the subject matter of the present invention unnecessarily unclear.

FIG. 1 is a flowchart for explaining a method for preparing an electrochemical catalyst according to a first embodiment of the present invention, and FIG. 2 is a view showing a process of preparing an electrochemical catalyst according to a second embodiment of the present invention.

Preparing a Base Structure

Referring to FIG. 1 , a base metal aqueous solution containing a base metal may be provided (S100). According to one embodiment, the providing of the base metal aqueous solution may include: preparing a source solution by mixing a base source containing a base metal with a solvent and mixing the source solution with polyvinylpyrrolidone. For example, the base metal may include cobalt (Co). For example, the base source may be cobalt(II) nitrate hexahydrate. For example, the solvent may be a solution in which ammonia water and distilled water (DI water) are mixed.

More specifically, the source solution may be prepared by mixing cobalt(II) nitrate hexahydrate having a concentration of 1.25 mmol with a solvent in which 50 ml of ammonia water and DI water are mixed at 3:1 vol %. After that, 0.1 g of polyvinylpyrrolidone was added to the prepared source solution and mixed at a speed of 600 rpm for 10 minutes to prepare the base metal aqueous solution.

A base structure containing an oxide of the base metal may be hydrothermally synthesized by using the base metal aqueous solution (S200). Specifically, for example, the base structure may be hydrothermally synthesized by transferring the base metal aqueous solution to an autoclave and heating it at a temperature of 180° C. for eight hours. As described above, when the base metal includes cobalt (Co), the base structure may include cobalt oxide (Co₃O₄). When a catalyst structure to be described later is prepared through the base structure including a cobalt oxide (Co₃O₄), the catalyst structure to be described later may be used as a catalyst for an oxygen evolution reaction (OER).

In contrast, according to another embodiment, the base metal may include molybdenum (Mo). In this case, the base structure may include a molybdenum oxide (MoO₃). Specifically, a base metal aqueous solution may be prepared by mixing sodium molybdate having a concentration of 10 mmol with 43 mL of distilled water (DI water), adding 2 ml of hydrochloric acid to the mixed solution, and then mixing at a speed of 500 rpm. After that, the base structure including a molybdenum oxide (MoO₃) may be prepared by transferring the base metal aqueous solution to a 70 mL Teflon-lined autoclave and heating at a temperature of 180° C. for 12 hours. When a catalyst structure to be described later is prepared through the base structure including a molybdenum oxide (MoO₃), the catalyst structure to be described later may be used as a catalyst for a hydrogen evolution reaction (HER).

In contrast, according to still another embodiment, the base metal may include tungsten (W). In this case, the base structure may include tungsten oxide (WO₃). Specifically, a base metal aqueous solution may be prepared by adding 10 mL of glycerol to 25 mL of distilled water, mixing at a speed of 1000 rpm for 30 minutes, adding 0.66 g of sodium tungstate dihydride to the resulting solution, and adding 2.5 mL of HCl (12 M). After that, the base structure including a tungsten oxide (WO₃) may be prepared by transferring the base metal aqueous solution to a 20 mL Teflon-lined autoclave and heating at a temperature of 180° C. for 90 hours. When a catalyst structure to be described later is prepared through the base structure including a tungsten oxide (WO₃), the catalyst structure to be described later may be used as a catalyst for a hydrogen evolution reaction (HER).

In contrast, according to still another embodiment, the base metal may include vanadium (V). In this case, the base structure may include vanadium oxide (V₂O₅). Specifically, a base metal aqueous solution may be prepared by mixing NH₄VO₅ having a concentration of 2 mmol with 45 ml of distilled water, adding 1 mL of HCl (1M) to the resulting solution, and mixing at a speed of 1000 rpm for 30 minutes. After that, a precipitate may be obtained from the base metal aqueous solution through a centrifugal separator (7000 rpm, 10 minutes), and the obtained precipitate may be washed and dried (60° C., 12 hours) to obtain a powder. Finally, the obtained powder may be heat-treated at a temperature of 550° C. for five minutes, thereby preparing the base structure including vanadium oxide (V₂O₅). When a catalyst structure to be described later is prepared through the base structure including a vanadium oxide (V₂O₅), the catalyst structure to be described later may be used as a catalyst for a hydrogen evolution reaction (HER).

Preparing of Catalyst Structure

Referring to FIGS. 1 and 2 , the base structure 110 may be heat-treated under a reaction gas atmosphere, thereby forming a catalyst structure 100 (S300). According to one embodiment, the reaction gas may include sulfur (S). For example, the reaction gas may be hydrogen sulfide (H₂S).

According to one embodiment, the catalyst structure 100 formed by heat-treating the base structure 110 including a cobalt oxide (Co₃O₄) under the reaction gas (H₂S) may include Co₃O₄, CoO, Co₃S₄, and CoS. In contrast, according to another embodiment, the catalyst structure 100 formed by heat-treating the base structure 110 including a molybdenum oxide (MoO₃) under the reaction gas (H₂S) may include MoO₂ and MoS₂. In contrast, according to still another embodiment, the catalyst structure 100 formed by heat-treating the base structure 110 including a tungsten oxide (WO₃) under the reaction gas (H₂S) may include WO₂ and WS₂. In contrast, according to still another embodiment, the catalyst structure 100 formed by heat-treating the base structure 110 including a vanadium oxide (V₂O₅) under the reaction gas (H₂S) may include VS₂.

Hereinafter, in describing the process of forming the catalyst structure 100 in detail, the base structure 110 including a cobalt oxide (Co₃O₄) will be exemplarily described.

When the reaction gas (e.g., H₂S) is heat-treated, the reaction gas may be decomposed into sulfur (S) and hydrogen (H) according to <Formula 1> below.

H₂S->H₂+S_(ad)  <Formula 1>

Sulfur (S) decomposed from the reaction gas may be adsorbed on a surface of the base structure 110. Sulfur (S) adsorbed on the surface of the base structure 110 may be exchanged with oxygen (O) on the surface of the base structure 110 according to <Formula 2> below. Accordingly, a preliminary shell structure 120 including a first base metal sulfide may be formed on the surface of the base structure 110. For example, the first base metal sulfide may be Co₃S₄.

CO₃O₄+4H₂+4S_(ad)->CO₃S₄+4H₂O  <Formula 2>

In addition, when continuously heat-treating the base structure 110 under the reaction gas atmosphere after the preliminary shell structure 120 is formed, a second base metal sulfide in which the first base metal sulfide is decomposed according to <Formula 3> below may be formed. For example, the second base metal sulfide may be CoS. Accordingly, the shell structure 140 including the first base metal sulfide (e.g., Co₃S₄) and the second base metal sulfide (e.g., CoS) will be formed on the surface of the base structure 110.

Co₃S₄->3 CoS+S  <Formula 3>

Unlike sulfur (S) decomposed from the reaction gas, hydrogen (H) decomposed from the reaction gas may penetrate the base structure 110. Hydrogen (H) penetrated an inside of the base structure 110 may be reacted with an oxide (e.g., Co₃O₄) of the base metal according to the following <Formula 4>. Accordingly, the base structure 110 may include a first base metal oxide, and a second base metal oxide in which the first base metal oxide may react with hydrogen (H) penetrated the inside of the base structure. For example, the first base metal oxide may be Co₃S₄, and the second base metal oxide may be CoO. In addition, a plurality of pores may be formed in the base structure 110 due to a reaction between the oxide of the base metal and hydrogen. The base structure 110 including the first base metal oxide (Co₃O₄) and the second base metal oxide (CoO) and formed with a plurality of pores may be defined as a core structure 130.

CO₃O₄+H₂->3CoO+H₂O  <Formula 4>

As a result, the catalyst structure 100 may include the core structure 130 having a porous structure, and the shell structure 140 formed on a surface of the core structure 130, in which the core structure 130 may include the first base metal oxide (Co₃O₄) and the second base metal oxide (CoO), and the shell structure 140 may include the first base metal sulfide (Co₃O₄) and the second base metal sulfide (CoS). Accordingly, the catalyst structure 100 may be used as a catalyst for an oxygen evolution reaction (OER), thereby improving oxygen generation efficiency.

According to one embodiment, in the catalyst structure 100, the content of the first and second base metal oxides (Co₃O₄, CoO) and the first and second base metal sulfides (Co₃O₄, CoO) may be controlled, and thus the oxygen generation efficiency of the catalyst structure 100 may be further improved.

According to one embodiment, during the process of preparing the catalyst structure 100, the temperature and time at which the base structure 110 is heat-treated under the reaction gas atmosphere (H₂S) may be controlled, and thus the content of the first and second base metal oxides (Co₃O₄, CoO) and the first and second base metal sulfides (Co₃O₄, CoO) may be controlled.

Specifically, the base structure 110 may be heat-treated at a temperature of 350° C. under the reaction gas atmosphere (H₂S) for 10 minutes or less. In this case, the catalyst structure 100 may include 49 wt % or more of the first base metal oxide (Co₃O₄), 40 wt % or less of the second base metal oxide (CoO), 11 wt % or less of the first base metal sulfide (Co₃O₄), and 0.5 wt % or less of the second base metal sulfide (CoS). The core structure 130 of the catalyst structure 100 having the above-described content may have a pore diameter of 12 nm or less. Accordingly, the catalyst structure 100 may improve oxygen generation efficiency when being used in an oxygen evolution reaction (OER).

In addition, as described above, in the method for preparing an electrochemical catalyst according to an embodiment of the present invention, hydrogen sulfide (H₂S) having high reducing power may be used in the process of preparing the catalyst structure 100, and thus a top-down synthesis method starting from bulk particles can be applied. Accordingly, the preparation process may be simplified and the method for preparing an electrochemical catalyst suitable for a large-scale production process may be provided.

As above, the electrochemical catalyst according to the first embodiment of the present invention and the method for preparing the same has been described. Hereinafter, the electrochemical catalyst according to a second embodiment of the present invention and a method for preparing the same will be described.

According to the second embodiment of the present invention, the electrochemical catalyst may include a base structure in a form of a flat plate including a metal, a first material layer formed on the surface of the base structure, and a second material layer formed on a surface of the first material layer. According to one embodiment, the metal may include any one of cobalt (Co), molybdenum (Mo), tungsten (W), or vanadium (V).

The first material layer may include an oxide of the metal. According to one embodiment, the first material layer may include a natural oxide layer of the metal. In contrast, the second material layer may include a sulfide of the metal. According to one embodiment, the second material layer may be a material layer formed by the same method as that of heat-treating the base structure 110 under the reaction gas (H₂S) atmosphere in the method for preparing an electrochemical catalyst according to the first embodiment, described with reference to FIGS. 1 and 2 . In other words, the second material layer may be formed by heat-treating the base structure, on which the first material layer is formed, under the reaction gas (H₂S) atmosphere.

The electrochemical catalyst according to the second embodiment may be used as a catalyst for an oxygen evolution reaction (OER) or a hydrogen evolution reaction (HER). In addition, like the method for preparing an electrochemical catalyst according to the first embodiment of the present invention, hydrogen sulfide (H₂S) having high reducing power may be used, and thus a top-down synthesis method starting from bulk particles may be applied. Accordingly, the preparation process may be simplified and may be easily applied to a large-scale production process.

As above, the electrochemical catalyst according to a second embodiment of the present invention and the method for preparing the same has been described. Hereinafter, specific experimental embodiments and the results of evaluating properties will be described with regard to the electrochemical catalyst according to an embodiment of the present invention.

Preparing the Electrochemical Catalyst According to Example 1

A source solution may be prepared by mixing cobalt(II) nitrate hexahydrate having a concentration of 1.25 mmol with a solvent in which 50 ml of ammonia water and distilled water (DI water) were mixed at 3:1 vol %. After that, 0.1 g of polyvinylpyrrolidone was added to the prepared source solution and mixed at a speed of 600 rpm for 10 minutes to prepare a base metal aqueous solution. The prepared base metal aqueous solution was transferred to a 70 mL Teflon-lined autoclave, and heated at a temperature of 180° C. for eight hours, and thus Co₃O₄ was hydrothermally synthesized. In addition, a precipitate was obtained from Co₃O₄ hydrothermally synthesized through a centrifugal separator (7000 rpm, 10 minutes), and the obtained precipitate was washed with DI water and ethanol, and then heat-treated in an oven at a temperature of 60° C. for 12 hours, to prepare a Co₃O₄ base structure.

Finally, the Co₃O₄ base structure was heat-treated (350° C., 10° C./min) under a gas atmosphere, in which argon (Ar) and hydrogen sulfide (H₂S) were mixed, and cooled in an N₂ gas atmosphere, to prepare an electrochemical catalyst according to Example 1 having a Co₃O₄—CoO core structure/Co₃S₄—CoS shell structure.

Preparing the Electrochemical Catalyst According to Example 2

A base metal aqueous solution was prepared by mixing sodium molybdate having a concentration of 10 mmol with 43 mL of distilled water (DI water), adding 2 ml of hydrochloric acid to the mixed solution, and then mixing at a speed of 500 rpm. After that, the base metal aqueous solution was transferred to a 70 mL Teflon-lined autoclave, and heated at a temperature of 180° C. for 12 hours, and thus MoO₃ was hydrothermally synthesized. In addition, a precipitate was obtained from MoO₃ hydrothermally synthesized through a centrifugal separator (7000 rpm, 10 minutes), and the obtained precipitate was washed with DI water and ethanol, and then heat-treated in an oven at a temperature of 60° C. for 12 hours, to obtain a MoO₃ powder. The obtained powder was heat-treated at a temperature of 500° C. for two hours to prepare a MoO₃ base structure. Finally, the MoO₃ base structure was heat-treated (350° C., 10° C./min, 60 minutes) under a gas atmosphere, in which argon (Ar) and hydrogen sulfide (H₂S) were mixed, and cooled in an N₂ gas atmosphere, to prepare an electrochemical catalyst according to Example 2 having a MoO₂ core structure/MoS₂ shell structure.

Preparing the Electrochemical Catalyst According to Example 3

A base metal aqueous solution was prepared by adding 10 mL of glycerol to 25 mL of distilled water, mixing at a speed of 1000 rpm for 30 minutes, adding 0.66 g of sodium tungstate dihydride to the resulting solution, and adding 2.5 mL of HCl (12 M). After that, the base metal aqueous solution was transferred to a 20 mL Teflon-lined autoclave, and heated at a temperature of 180° C. for minutes, and thus WO₃ was hydrothermally synthesized. In addition, a precipitate was obtained from WO₃ hydrothermally synthesized through a centrifugal separator (7000 rpm, 10 minutes), and the obtained precipitate was washed with distilled water (DI water) and ethanol, and then heat-treated in an oven at a temperature of 60° C. for 12 hours, to obtain a WO₃ powder. The obtained powder was heat-treated at a temperature of 500° C. for two hours to prepare a WO₃ base structure.

Finally, the WO₃ base structure was heat-treated (350° C., 10° C./min, 60 minutes) under a gas atmosphere, in which argon (Ar) and hydrogen sulfide (H₂S) were mixed, and cooled in an N₂ gas atmosphere, to prepare an electrochemical catalyst according to Example 3 having a WO₃ core structure/WS₂ shell structure.

Preparing the Electrochemical Catalyst According to Example 4

A base metal aqueous solution was prepared by mixing NH₄VO₅ having a concentration of 2 mmol with 45 ml of distilled water, adding 1 mL of HCl (1M) to the resulting solution, and mixing at a speed of 1000 rpm for 30 minutes. After that, a precipitate was obtained from the base metal aqueous solution through a centrifugal separator (7000 rpm, 10 minutes), and the obtained precipitate was washed and dried (60° C., 12 hours) to obtain a powder. Finally, the obtained powder was heat-treated at a temperature of 550° C. for five minutes, thereby preparing the base structure including vanadium oxide (V₂O₅).

Finally, the V₂O₅ base structure was heat-treated (300° C., 10° C./min, 30 minutes) under a gas atmosphere, in which argon (Ar) and hydrogen sulfide (H₂S) were mixed, and cooled in an N₂ gas atmosphere, to prepare an electrochemical catalyst according to Example 4 having a bulk VS₂ structure.

The electrochemical catalysts according to above Examples 1 to 4 are summarized in <Table 1> below.

TABLE 1 Base Classification structure Catalyst structure Example 1 Co₃O₄ Co₃O₄—CoO core structure/ Co₃S₄—CoS shell structure Example 2 MoO₃ MoO₂ core structure/MoS₂ shell structure Example 3 WO₃ WO₃ core structure/WS₂ shell structure Example 4 V₂O₅ Bulk VS₂

FIG. 3 is a view showing SEM images of a catalyst structure and a base structure according to Example 1 of the present invention. Referring to (a) and (b) of FIGS. 3 , a scanning electron microscope (SEM) image of the base structure provided in the process of preparing the catalyst structure according to above Example 1 is shown, and referring to (c) to (n) of FIGS. 3 , the catalyst structure according to above Example 1 was provided, but a heat-treatment time is controlled to be 10, 20, 30, 40, 50, and 60 minutes to prepare a plurality of catalyst structures formed, after which SEM images for each are shown.

As can be understood from (a) to (n) of FIG. 3 , it could be confirmed that the Co₃O₄ base structure has an average size of 700 nm and a spherical shape, which is maintained despite an increase in the heat treatment time. In addition, it could be confirmed that a Co₃S₄—CoS shell structure is formed on the surface of the base structure as the base structure is heat-treated under a hydrogen sulfide (H₂S) atmosphere.

Alternatively, with regard to the above-described base structure and the catalyst structures prepared at different heat treatment times, respectively, a Brunauer-Emmett-Teller (BET) surface area (a_(s,BET)), a total pore volume, and mean pore diameters were measured and the results thereof are summarized in <Table 2> below.

TABLE 2 Total pore volume Mean pore a_(s, BET) (p/p₀ = 0.990) diameter Classification (m²/g) (cm³/g) (nm) Base structure 1.449 0.01 27.754 Catalyst 6.134 0.017 11.688 structure (heat-treated for 10 minutes) Catalyst 6.846 0.023 13.221 structure (heat-treated for 20 minutes) Catalyst 3.551 0.014 15.647 structure (heat-treated for 30 minutes) Catalyst 2.383 0.0125 20.976 structure (heat-treated for 40 minutes) Catalyst 2.257 0.012 20.457 structure (heat-treated for 50 minutes) Catalyst 2.189 0.011 20.509 structure (heat-treated for 60 minutes)

As can be understood from <Table 2>, it could be confirmed that the BET surface area of the catalyst structure increases compared to the base structure. In particular, it could be confirmed that the BET surface area increases while the heat treatment time increases from 10 to 20 minutes, but the BET surface area gradually decreases when the heat treatment time exceeds 20 minutes. Accordingly, it can be seen that the degree of sulfidation of the catalyst structure increases as the heat treatment time increases. FIG. 4 is a view showing TEM images of a catalyst structure and a base structure according to Example 1 of the present invention.

Referring to (a) and (b) of FIG. 4 , a transmission electron microscope (TEM) image of the base structure prepared in the process of preparing the catalyst structure according to above Example 1 is shown. Referring to (c) and (d) of FIG. 4 , a TEM image of the catalyst structure according to above Example 1 formed by heat treatment for 10 minutes is shown. Referring to (e) and (f) of FIG. 4 , a TEM image of the catalyst structure according to above Example 1 formed by heat treatment for 20 minutes is shown. Referring to (g) and (h) of FIG. 4 , a TEM image of the catalyst structure according to above Example 1 formed by heat treatment for 30 minutes is shown. Referring to (i) and (j) of FIG. 4 , a TEM image of the catalyst structure according to above Example 1 formed by heat treatment for 40 minutes is shown. Referring to (k) and (l) of FIG. 4 , a TEM image of the catalyst structure according to above Example 1 formed by heat treatment for 50 minutes is shown. And, referring to (m) and (n) of FIG. 4 , a TEM image of the catalyst structure according to above Example 1 formed by heat treatment for 60 minutes is shown. (a), (c), (e), (g), (i), (k), and (m) of FIG. 4 represent a bright-field of the TEM, and (b), (d), (f), (h), (j), (l), and (n) of FIG. 4 represent a dark-field of TEM.

In addition, (o) and (q) of FIG. 4 represents an HRTEM image of the base structure provided in the process of preparing the catalyst structure according to above Example 1, and (q) and (r) of FIG. 4 represent an FFT pattern of the catalyst structure according to above Example 1 formed by heat treatment for 10 minutes.

As can be understood from (a) to (n) of FIG. 4 , it could be confirmed that the catalyst structure has a core-shell structure, and the thickness of the shell increases as the heat treatment time increases. In addition, as can be understood from (o) to (q) of FIG. 4 , it could be confirmed that lattice fingers with a d spacing of 4.7028, 3.3254, 2.8359, and 2.7151 A° correspond to (2 0 0), (0 2 2), (3 1 1), and (2 2 2) planes of the base structure (Co₃O₄).

FIG. 5 is a view showing TEM images and EDS mapping images of a catalyst structure according to Example 1 of the present invention.

Referring to (a) of FIG. 5 , a dark-field TEM image of the catalyst structure according to above Example 1 formed by heat treatment for 10 minutes is shown. Referring to (b) to (d) of FIG. 5 , an EDS mapping image of the catalyst structure according to above Example 1 formed by heat treatment for 10 minutes is shown. Referring to (g) of FIG. 5 , a dark-field TEM image of the catalyst structure according to above Example 1 formed by heat treatment for 60 minutes is shown. And, referring to (h) to (j) of FIG. 5 , an EDS mapping image of the catalyst structure according to above Example 1 formed by heat treatment for 10 minutes is shown.

In addition, referring to (e) and (k) of FIG. 5 , a line profile of the catalyst structure according to above Example 1 formed by heat treatment for 10 to 60 minutes is shown, respectively. And, referring to (f) and (l) of FIG. 5 , a weight percentage of cobalt, oxygen, and sulfur in the catalyst structure according to above Example 1 formed by heat treatment for 10 to 60 minutes is shown, respectively.

As can be understood from (a) to (j) of FIG. 5 , it could be confirmed that sulfur (S) is present only on the surface of the Co₃O₄ base structure, and an amount of sulfur (S) present on the surface increases as the heat treatment time increases.

FIG. 6 is a view showing the results of XRD analysis of a catalyst structure and a base structure according to Example 1 of the present invention.

Referring to FIG. 6 , X-ray diffraction (XRD) analysis was performed to measure the crystal structure, crystallinity, and phase of the base structure provided in the process of preparing the catalyst structure according to Example 1 and the catalyst structures according to Example 1 formed by controlling the heat-treatment time to be 10, 20, 30, 40, 50, and 60 minutes, and the results thereof are shown (Co₃O₄: red, CoO: orange, CoS: green, Co₃S₄: blue).

As can be understood from FIG. 6 , it could be confirmed that all of the plurality of catalyst structures formed at different heat treatment times exhibit a diffraction peak of Co₃O₄ [JCPDS #42-1467], CoO [JCPDS #43-1004], CoS [JCPDS #73-1703] and Co₃S₄ [JCPDS #75-0605]. In addition, it could be confirmed that Co₃O₄ is converted to CoO, and peaks of CoS and Co₃S₄ newly appear as the base structure is heat-treated under hydrogen sulfide (H₂S).

The composition and grain size of the above-described base structure and a plurality of catalyst structures are summarized in <Table 3> below.

TABLE 3 Classifi- cation Co₃O₄ CoO CoS Co₃S₄ GOF R_(wp) Base Grain 54.58 — — — 1.07 4.07 structure size (nm) Catalyst Ratio 49.55% 39.94% 0.40% 10.12% 1.02 2.73 structure Grain 22.07 8.56 — 16.14 (10 size minutes) (nm) Catalyst Ratio 36.11% 47.75% 0.83% 15.31% 1 2.89 structure Grain 21.15 8.25 — 14.9 (20 size minutes) (nm) Catalyst Ratio 12.85% 45.07% 10.45% 31.63% 1.01 2.85 structure Grain 22.33 9.65 5.52 13.74 (30 size minutes) (nm) Catalyst Ratio 9.73% 40.82% 17.61% 31.84% 1.06 3.3 structure Grain 23.74 9.13 3.28 16.63 (40 size minutes) (nm) Catalyst Ratio 3.38% 16.65% 26.62% 53.35% 1.04 3.16 structure Grain 16.26 9.9 7.6 16.23 (50 size minutes) (nm) Catalyst Ratio 2.77% 12.87% 16.76% 67.61% 1.04 2.77 structure Grain 23.52 11.6 9.19 18.57 (60 size minutes) (nm)

FIG. 7 is a graph showing an area of a catalyst structure and a base structure according to Example 1 of the present invention. Referring to (a) and (b) of FIG. 7 , after providing the base structure provided in the process of preparing the catalyst structure according to above Example 1 and the catalyst structures according to above Example 1 formed by controlling the heat-treatment time to be 10, 20, 30, 40, 50, and 60 minutes, each surface area and pore size distribution were measured and shown. Specifically, the surface area was measured by using the Brunauer-Emmett-Teller (BET) method, and the pore size distribution was measured by using the Barrett-Joyner-Halenda (BJH) method. As can be understood from (a) to (b) of FIG. 7 , it could be confirmed that the surface area and pore size distribution of the catalyst structure changes as the heat treatment time is changed.

FIGS. 8 to 10 are views showing results of XPS analysis of a catalyst structure and a base structure according to Example 1 of the present invention.

Referring to (a) to (d) of FIG. 8 , Co 2p spectra of the base structure provided in the process of preparing the catalyst structure according to above Example 1 and the catalyst structure according to above Example 1 formed by controlling the heat-treatment time to be 10, 30, and 60 minutes are shown.

Referring to (a) to (c) of FIG. 9 , S 2p spectra of the catalyst structure according to above Example 1 formed by controlling the heat-treatment time to be 10, 30, and 60 minutes are shown.

Referring to (a) to (d) of FIG. 10 , O 1s spectra of the base structure provided in the process of preparing the catalyst structure according to above Example 1 and the catalyst structure according to above Example 1 formed by controlling the heat-treatment time to be 10, 30, and 60 minutes are shown.

As can be understood from (a) to (d) of FIG. 8 , it could be confirmed that the Co 2p spectrum is separated into a spin-orbital doublet, which is a property of Co³⁺ and Co²⁺, together with two satellite peaks. Alternatively, as can be understood from (a) of FIG. 8 , it could be confirmed that the Co₃O₄ base structure shows a peak corresponding to Co³⁺ at binding energy values of 779.5 eV and 794.6 eV, and a peak corresponding to Co²⁺ at binding energy values of 781.8 eV and 797 eV. Alternatively, as can be understood from (b) to (d) of FIG. 8 , it could be confirmed that the Co₃O₄—CoO/Co₃S₄—CoS catalyst structure shows a peak corresponding to Co³⁺ at binding energy values of 778.2 eV and 793.3 eV, and a peak corresponding to Co²⁺ at binding energy values of 780.9 eV and 796.8 eV. Alternatively, as can be understood from (a) to (c) of FIG. 9 , Co—S bonding could be confirmed through a peak at 161.2 eV and 162.4 eV. Accordingly, it can be seen that the Co—S bond is formed, and Co₃O₄ is reduced and sulfided.

Manufacturing of a Three-Electrode System for Measuring Electrochemical Properties of Catalyst Structure According to Example 1

The electrochemical properties in the oxygen evolution reaction (OER) were measured by forming three electrodes with a glassy carbon (GC) working electrode including an active catalyst, a Pt wire counter electrode, and a Hg/HgO reference electrode, and by using linear sweep voltammetry (LSV) with KOH at a 1 M concentration and a scan rate of 10 mv/s.

In the process of manufacturing working electrodes, specifically, 5 mg of an active catalyst, a solvent of DI water and ethanol mixed at a ratio of 1:1, and 5 wt % of Nafion were subjected to sonication for two hours, thereby preparing a solution. 10 μL of the prepared solution was added dropwise to polished glassy carbon (GC) having a diameter of 3 mm and dried at room temperature to prepare a working electrode.

A base structure (Co₃O₄) provided in the process of preparing the catalyst structure according to Example 1, Co₃O₄/CoO structure, catalyst structures according to above Example 1 formed by controlling the heat-treatment time to be 10, 20, 30, 40, 50, and 60 minutes, and iridium oxide (IrO₂) were used as an active catalyst. Alternatively, as a control group, glassy carbon (GC) without containing an active catalyst was used as a working electrode.

FIG. 11 is a view showing the electrochemical properties of a catalyst structure and a base structure according to Example 1 of the present invention.

(a) of FIG. 11 shows polarization curves, (b) of FIG. 11 shows a Tafel plot, (c) of FIG. 11 shows a change in current density according to a scan rate, and (d) of FIG. 11 shows a Nyquist plot.

As can be understood from (a) of FIG. 11 , it could be confirmed that overpotentials of 546 mV and 416 mV appear when the Co₃O₄ base structure according to above Example 1, and the Co₃O₄/Co₀ structure are used as active catalysts. In addition, it could be confirmed that overpotentials of 320 mV, 350 mV, 469 mV, 486 mV, 513 mV, and 526 mV appear when catalyst structures according to above Example 1 formed by heat treatment for 10, 20, 30, 40, 50, and 60 minutes are used as active catalysts. Furthermore, it could be confirmed that an overpotential of 347 mV appears when the iridium oxide (IrO₂) is used as an active catalyst.

In particular, it could be seen that the catalyst structure (320 mV) according to above Example 1 formed by heat treatment for 10 minutes shows an overpotential lower than that of the iridium oxide (347 mV), thus providing excellent electrochemical properties.

As can be understood from (b) of FIG. 11 , it could be confirmed that Tafel slope values of 121 mV/dec and 83 mV/dec appear when the Co₃O₄ base structure according to above Example 1 and the Co₃O₄/CoO structure are used as active catalysts. In addition, it could be confirmed that Tafel slope values of 65 mV/dec, 71 mV/dec, 100 mV/dec, 102 mV/dec, 109 mV/dec, and 115 mV/dec appear when catalyst structures according to the above Example 1 formed by heat treatment for 10, 20, 30, 40, 50, and 60 minutes are used as active catalysts. Furthermore, it could be confirmed that a Tafel slope value of 70 mV/dec appears when the iridium oxide (IrO₂) is used as an active catalyst.

In particular, it could be seen that the catalyst structure (65 mV/dec) according to above Example 1 formed by heat treatment for 10 minutes shows a Tafel slope value lower than that of the iridium oxide (70 mV/dec), thus providing excellent electrochemical properties.

As can be understood from (d) of FIG. 11 , it could be confirmed that charge transfer resistance values of 2044Ω and 222.4Ω appear when the Co₃O₄ base structure according to above Example 1, and the Co₃O₄/CoO structure are used as active catalysts. In addition, it could be confirmed that charge transfer resistance values of 42 Ω, 103 Ω, 882 Ω, 1300 Ω, 1720Ω, and 1894Ω appear when catalyst structures according to above Example 1 formed by heat treatment for 10, 20, 30, 40, 50, and 60 minutes are used as active catalysts. Furthermore, it could be confirmed that a charge transfer resistance value of 59Ω appears when the iridium oxide (IrO₂) is used as an active catalyst.

In particular, it could be seen that the catalyst structure (42Ω) according to above Example 1 formed by heat treatment for 10 minutes shows a charge transfer resistance value lower than that of the iridium oxide (59Ω), thus providing excellent electrochemical properties.

The values measured in FIG. 11 are summarized in <Table 4> below.

TABLE 4 Exchange Charge Over- current transfer Tafel potential(η) density j₀ mA resistance slope mV at 10 mA cm⁻²@over- R_(ct) Classification mV/dec cm⁻² potential(η) = 0 ohm Base 121 546 0.301 2044 structure Catalyst 65 320 1.258 42.7 structure (10 minutes) Catalyst 71 350 0.971 103.7 structure (20 minutes) Catalyst 100 469 0.467 882.5 structure (30 minutes) Catalyst 102 486 0.396 1300 structure (40 minutes) Catalyst 109 513 0.333 1720 structure (50 minutes) Catalyst 115 526 0.329 1894 structure (60 minutes) Iridium 70 347 0.926 59.7 oxide (IrO₂)

In addition, the turnover frequency (TOF) of the above-described active catalysts at an overpotential of 400 mV was calculated according to <Equation 1> below, and the results thereof are summarized in <Table 5> below. <Equation 1>

TOF=j×A/4×F×n

(j: Geometric current density measured at an overpotential of 400 mV, A: Surface area of GC working electrode, F: Faraday constant, n: Number of moles of active catalyst provided to GC working electrode)

TABLE 5 Classification TOF(S⁻¹) η = 400 mV Base structure 2.3 × 10⁻⁴ Catalyst structure (10 minutes) 1.3 × 10⁻² Catalyst structure (20 minutes) 8.1 × 10⁻³ Catalyst structure (30 minutes) 1.0 × 10⁻³ Catalyst structure (40 minutes) 1.2 × 10⁻³ Catalyst structure (50 minutes) 1.2 × 10⁻³ Catalyst structure (60 minutes) 8.35 × 10⁻⁴  Iridium oxide (IrO₂) 2.4 × 10⁻²

As a result, it can be seen that the properties of the electrochemical catalyst may be improved by controlling the heat treatment temperature of the base structure to be 10 minutes or less in the process of preparing the electrochemical catalyst according to an embodiment of the present invention. In particular, as can be understood from <Table 2> and <Table 3> described above, it can be seen that the catalyst structure according to Example 1 formed at a heat treatment temperature of 10 minutes includes 49 wt % or more of Co₃O₄, 40 wt % or less of CoO, 11% or less of Co₃S₄, and 0.5% or less of CoS, and average pore size is 12 nm or less. FIGS. 12 to 15 are graphs showing electrochemically active surface areas of a catalyst structure and a base structure according to Example 1 of the present invention.

Referring to FIGS. 12 to 15 , the electrochemical active surface areas (ECSA) of the active catalyst were calculated by extracting a double-layer capacitance (C_(d1)) through cyclic voltammetry (CV) measurement in the cases of not applying an active catalyst, applying the base structure (Co₃O₄) according to above Example 1 as an active catalyst, applying the Co₃O₄/CoO structure as an active catalyst, applying the catalyst structures according to above Example 1 formed by controlling the heat-treatment time to be 10, 20, 30, 40, 50, and 60 minutes, and applying the iridium oxide (IrO₂) as an active catalyst.

The electrochemical active surface areas (ECSA) were calculated through <Equation 2> and <Equation 3>.

ECSA=R _(f) ×A  <Equation 2>

R _(f) =C _(d1) /C _(s)  <Equation 3>

(Rf: Roughness coefficient calculated from the ratio of double-layer capacitance (C_(d1)) of each active catalyst and GC working electrode (C_(s)), A: Geometric area of GC working electrode surface (0.07 cm²))

Specifically, (a) to (c) of FIG. 12 show the cases of not applying an active catalyst, applying the Co₃O₄ base structure according to above Example 1 as an active catalyst, and applying the Co₃O₄/CoO structure as an active catalyst. (a) to (c) of FIG. 13 show the case of applying the catalyst structure according to above Example 1 formed by heat treatment for 10, 20, and 30 minutes as an active catalyst. (a) to (c) of FIG. 14 show the case of applying the catalyst structure according to above Example 1 formed by heat treatment for 40, 50, and 60 minutes as an active catalyst. FIG. 14 shows the case of applying the iridium oxide (IrO₂) as an active catalyst. The measured values are summarized in <Table 6> below.

TABLE 6 Slope C_(dl) ECSA Classification (mF cm⁻²) (mF cm⁻²) Rf cm² Active 0.204 0.102 — — catalyst X Base 0.492 0.246 2.4 0.16 structure Co₃O₄/CoO 1.38 0.69 6.76 0.47 Catalyst 3.12 1.56 15.3 1.07 structure (10 minutes) Catalyst 1.31 0.655 6.4 0.45 structure (20 minutes) Catalyst 0.762 0.381 3.7 0.26 structure (30 minutes) Catalyst 0.740 0.370 3.6 0.25 structure (40 minutes) Catalyst 0.658 0.329 3.2 0.22 structure (50 minutes) Catalyst 0.533 0.266 2.6 0.18 structure (60 minutes) IrO₂ 5.86 2.93 28.7 2.0

As can be understood from <Table 6>, it could be confirmed that the ECSA value and the number of active sites significantly decrease as the heat treatment time increases. FIG. 16 is a graph showing the stability of a catalyst structure according to Example 1 of the present invention.

Referring to FIG. 16 , the catalyst structure according to above Example 1 formed by heat treatment for 10 minutes may be prepared. After preparing a three-electrode system in which the provided catalyst structure was applied as an active catalyst, 1000 CV cycles were performed from 1.23V to 1.63V (RHE) at a scan rate of 100 mv/s.

As can be understood from FIG. 16 , it could be confirmed that the current density at 1.7V decreases by about 10% from 60.05 mA/cm² to 54.1 mA/cm² during 1000 CV cycles. In other words, it could be confirmed that the catalyst structure according to above Example 1 formed by heat treatment for 10 minutes has high stability.

FIG. 17 is a view showing FE-SEM images of a catalyst structure and a base structure according to Example 2 of the present invention, FIG. 18 is a view showing TEM images of a catalyst structure and a base structure according to Example 2 of the present invention, and FIG. 19 is a view showing EDS mapping images of a catalyst structure according to Example 2 of the present invention.

Referring to (a) of FIG. 17 , an FE-SEM image of the base structure (MoO₃) according to above Example 2 is shown and referring to (b) of FIG. 17 , an FE-SEM image of the catalyst structure (MoO₂/MoS₂) according to above Example 2 is shown. As can be understood from (a) and (b) of FIG. 17 , it could be confirmed that the MoO₃ base structure has a rod shape, and a MoS₂ shell is formed on the surface of the base structure as the base structure is heat-treated under a hydrogen sulfide (H₂S) atmosphere.

Referring to (a) and (e) of FIG. 18 , bright-field TEM images of the base structure (MoO₃) and the catalyst structure (MoO₂/MoS₂) according to above Example 2 are shown, and referring to (b) and (f) of FIG. 18 , dark-field TEM images of the base structure (MoO₃) and the catalyst structure (MoO₂/MoS₂) according to above Example 2 are shown. In addition, referring to (c) and (g) of FIG. 18 , HRTEM images of the base structure (MoO3) and the catalyst structure (MoO₂/MoS₂) according to above Example 2 are shown, and referring to (d) and (h) of FIG. 18 , FFT patterns of the base structure (MoO₃) and the catalyst structure (MoO₂/MoS₂) according to above Example 2 are shown. As can be understood from (a) to (h) of FIG. 18 , it could be confirmed that the catalyst structure according to above Example 2 has a structure of MoO₂ core structure/MoS₂ shell structure.

Referring to (a) to (e) of FIG. 19 , EDS mapping images of the catalyst structure according to above Example 2 are shown. As can be understood from (a) to (e) of FIG. 19 , it could be confirmed that the catalyst structure according to above Example 2 is formed with sulfur (S), molybdenum (Mo), and oxygen (O).

FIG. 20 is a view showing results of XRD analysis of a catalyst structure and a base structure according to Example 2 of the present invention, and FIG. 21 is a view showing an area of a catalyst structure and a base structure according to Example 2 of the present invention.

Referring to FIG. 20 , an XRD analysis was performed on the base structure (MoO₃) and the catalyst structure (MoO₂/MoS₂) according to above Example 2, and the results thereof are shown (MoO₃: red, MoO₂: green, MoS₂: blue). As can be understood from FIG. 20, it could be confirmed that MoS₃ is changed to MoS₂ and thus MoS₂ is produced as the base structure is heat-treated in a hydrogen sulfide (H₂S) atmosphere.

Referring to (a) of FIG. 21 , a surface area of the base structure (MoO₃) and the catalyst structure (MoO₂/MoS₂) according to above Example 2 was measured and shown by using the Brunauer-Emmett-Teller (BET) method, and referring to (b) of FIG. 21 , a pore size distribution of the base structure (MoO₃) and the catalyst structure (MoO₂/MoS₂) according to above Example 2 was measured and shown by using the Barrett-Joyner-Halenda (BJH) method. The measured results are summarized in <Table 7> below.

TABLE 7 Total pore volume Mean pore a_(s, BET) (p/p₀ = 0.990) diameter Classification (m²/g) (cm³/g) (nm) Base structure 0.656 0.005 33 Catalyst 4.521 0.027 24.2 structure

As can be understood from <Table 7>, it could be confirmed that a surface area (a_(s,BET)) is widened and a mean pore diameter is decreased as the base structure is heat-treated under hydrogen sulfide (H₂S).

Manufacturing of a Three-Electrode System for Measuring Electrochemical Properties of Catalyst Structure According to Example 2

The electrochemical properties in the hydrogen evolution reaction (HER) were measured by forming three electrodes with a glassy carbon (GC) working electrode including an active catalyst, a Pt gauze counter electrode, and a saturated calomel electrode (SCE) as a reference electrode, and by using CHI 660D at H₂SO₄ at a 0.5 M concentration.

The base structure (MoO₃) and the catalyst structure (MoO₂/MoS₂) according to above Example 2 were used as active catalysts. Alternatively, as a control group, glassy carbon (GC) without containing an active catalyst was used as a working electrode.

FIGS. 22 to 24 are views showing electrochemical properties of a catalyst structure and a base structure according to Example 2 of the present invention.

(a) of FIG. 22 shows a polarization curve, (b) of FIG. 22 shows a Tafel plot, (a) of FIG. 23 shows a change in current density according to a scan rate, (b) of FIG. 23 shows a Nyquist plot, and FIG. 24 shows an overpotential (mV) when using the base structure and the catalyst structure according to above Example 2 as an active catalyst. In addition, the turnover frequency (TOF) of the above-described active catalysts at an overpotential of 400 mV was calculated. The result values measured in FIGS. 22 to 24 are summarized in <Table 8> below, and the TOF values are summarized in <Table 9> below.

TABLE 8 Exchange Charge Over- current transfer Tafel potential(η) density j₀ mA resistance slope mV at 10 mA cm⁻²@over- R_(ct) Classification mV/dec cm⁻² potential(η) = 0 ohm Base 123 608 1.09 × 10⁻⁴ 163.1 structure Catalyst 112 308 0.03 35.9 structure

TABLE 9 Classification TOF(S⁻¹) η = 400 mV Base structure 2.64 × 10⁻⁵ Catalyst structure  5.8 × 10⁻³

FIG. 25 is a graph showing electrochemically active surface areas and stability of a catalyst structure and a base structure according to Example 2 of the present invention. Referring to (a) to (c) of FIG. 25 , the electrochemical active surface areas (ECSA) of the active catalyst were calculated by extracting a double-layer capacitance (C_(d1)) through cyclic voltammetry (CV) measurement in the cases of not applying an active catalyst, applying the base structure (MoO₃) according to above Example 2 as an active catalyst, and applying the catalyst structure (MoO₂/MoS₂) according to above Example 2. The calculated results are summarized in <Table 10> below.

TABLE 10 Slope C_(dl) ECSA Classification (mF cm⁻²) (mF cm⁻²) Rf cm² Active 0.121 0.0607 — — catalyst x Base 0.402 0.2012 3.31 0.23 structure Catalyst 3.39 1.695 27.92 1.95 structure

Referring to (d) of FIG. 25 , the catalyst structure according to above Example 2 may be provided. After preparing a three-electrode system in which the provided catalyst structure was applied as an active catalyst, 1000 CV cycles were performed and stability was measured. As can be understood from (d) of FIG. 25 , it could be confirmed that a current density remains substantially constant during 1000 CV cycles. FIG. 26 is a view showing FE-SEM images of a base structure according to Example 3 of the present invention, FIG. 27 is a view showing FE-SEM images of a catalyst structure according to Example 3 of the present invention, and FIG. 28 is a view showing TEM images of a catalyst structure and a base structure according to Example 3 of the present invention.

Referring to (a) and (b) of FIG. 26 , an FE-SEM image of the base structure (WO₃) according to Example 3 is shown. Referring to (a) and (b) of FIG. 27 , an FE-SEM image of the catalyst structure (WO₃/WS₂) according to above Example 3 is shown. And, referring to (a) to (d) of FIG. 28 , a TEM image of the catalyst structure (WO₃/WS₂) according to above Example 3 is shown. As can be understood from FIGS. 26 to 28 , it could be confirmed that the catalyst structure according to above Example 3 has a WS₂ shell structure formed on the surface of the WO₃ base structure.

FIG. 29 is a view showing results of XRD analysis of a catalyst structure and a base structure according to Example 3 of the present invention, and FIG. 30 is a view showing an area of a catalyst structure and a base structure according to Example 3 of the present invention.

Referring to FIG. 29 , an XRD analysis was performed on the base structure (WO₃) and the catalyst structure (WO₃/WS₂) according to above Example 3, and the results thereof are shown (Bulk WO₃: black, WO₃ Monoclinic: red, WS₂: blue). As can be understood from FIG. 29 , it could be confirmed that WS₂ is produced as the base structure is heat-treated in a hydrogen sulfide (H₂S) atmosphere.

Referring to (a) of FIG. 30 , a surface area of the base structure (WO₃) and the catalyst structure (WO₃/WS₂) according to above Example 3 was measured and shown by using the Brunauer-Emmett-Teller (BET) method, and referring to (b) of FIG. 30 , a pore size distribution of the base structure (WO₃) and the catalyst structure (WO₃/WS₂) according to above Example 2 was measured and shown by using the Barrett-Joyner-Halenda (BJH) method. The measured results are summarized in <Table 11> below.

TABLE 11 Total pore volume Mean pore a_(s), _(BET) (p/p₀ = 0.990) diameter Classification (m²/g) (cm³/g) (nm) Base structure 6.5009 0.089212 54.892 Catalyst 9.3899 0.1245 53.038 structure

As can be understood from <Table 11>, it could be confirmed that a surface area (a_(s,BET)) is widened and a mean pore diameter is decreased as the base structure is heat-treated under hydrogen sulfide (H₂S). FIGS. 31 to 33 are views showing electrochemical properties of a catalyst structure and a base structure according to Example 3 of the present invention.

(a) of FIG. 31 shows a polarization curve, (b) of FIG. 31 shows a Tafel plot, (a) of FIG. 32 shows a change in current density according to a scan rate, (b) of FIG. 32 shows a Nyquist plot, and FIG. 33 shows an overpotential (mV) when using the base structure and the catalyst structure according to Example 3 as an active catalyst. In addition, the turnover frequency (TOF) of the above-described active catalysts at an overpotential of 400 mV was calculated. The result values measured in FIGS. 31 to 33 are summarized in <Table 12> below, and the TOF values are summarized in <Table 13> below.

TABLE 12 Exchange Charge Over- current transfer Tafel potential(η) density j₀ mA resistance slope mV at 10 mA cm⁻²@over- R_(ct) Classification mV/dec cm⁻² potential(η) = 0 ohm Base 138 718 0.5 × 10⁻⁴ 925 structure Catalyst 116 525 0.0046 134 structure

TABLE 13 Classification TOF(S⁻¹) η = 400 mV Base structure 1.1 × 10⁻⁴ Catalyst structure 4.7 × 10⁻³

FIG. 34 is a graph showing electrochemically active surface areas and stability of a catalyst structure and a base structure according to Example 2 of the present invention. Referring to (a) to (c) of FIG. 34 , the electrochemical active surface areas (ECSA) of the active catalyst were calculated by extracting a double-layer capacitance (C_(d1)) through cyclic voltammetry (CV) measurement in the cases of not applying an active catalyst, applying the base structure (WO₃) according to above Example 3 as an active catalyst, and applying the catalyst structure (WO₃/WS₂) according to above Example 3. The calculated results are summarized in <Table 14> below.

TABLE 14 Slope C_(dl) ECSA Classification (mF cm⁻²) (mF cm⁻²) Rf cm² Active 0.121 0.0607 — — catalyst x Base 1.06 0.53 8.73 0.611 structure Catalyst 1.25 0.625 10.29 0.72 structure

FIG. 35 is a view showing FE-SEM images of a base structure according to Example 4 of the present invention, and FIG. 36 is a view showing FE-SEM images of a catalyst structure according to Example 4 of the present invention. Referring to (a) and (b) of FIG. 35 , an FE-SEM image of the base structure (V₂O₅) according to above Example 4 is shown, and referring to (a) and (b) of FIG. 36 , an FE-SEM image of the catalyst structure (VS₂) according to above Example 4 is shown. As can be understood from FIGS. 35 and 36 , it could be confirmed that the catalyst structure (VS₂) is formed as the base structure (V₂O₅) is heat-treated in a hydrogen sulfide (H₂S) atmosphere.

FIG. 37 is a view showing results of XRD analysis of a catalyst structure and a base structure according to Example 4 of the present invention, and FIG. 38 is a view showing an area of a catalyst structure and a base structure according to Example 4 of the present invention.

Referring to FIG. 37 , XRD analysis was performed on the base structure (V₂O₅) and the catalyst structure (VS₂) according to above Example 4, and the results thereof are shown (Bulk V₂O₅: black, VS₂: blue). As can be understood from FIG. 37 , it could be confirmed that the catalyst structure (VS₂) is formed as the base structure (V₂O₅) is heat-treated in a hydrogen sulfide (H₂S) atmosphere.

Referring to (a) of FIG. 38 , a surface area of the base structure (V₂O₅) and the catalyst structure (VS₂) according to above Example 4 was measured and shown by using the Brunauer-Emmett-Teller (BET) method, and referring to (b) of FIG. 38 , a pore size distribution of the base structure (V₂₀₅) and the catalyst structure (VS₂) according to above Example 4 was measured and shown by using the Barrett-Joyner-Halenda (BJH) method. The measured results are summarized in <Table 15> below.

TABLE 15 Total pore volume Mean pore a_(s, BET) (p/p₀ = 0.990) diameter Classification (m²/g) (cm³/g) (nm) Base structure 14.872 0.0556 14.9 Catalyst 9.7641 0.0277 11.3 structure

As can be understood from <Table 15>, it could be confirmed that a surface area (a_(s,BET)) and a mean pore diameter are decreased as the base structure is heat-treated under hydrogen sulfide (H₂S). FIG. 39 is a view showing electrochemical properties of a catalyst structure and a base structure according to Example 4 of the present invention.

(a) of FIG. 39 represents a polarization curve and (b) of FIG. 39 represents a Tafel plot. As can be understood from (a) and (b) of FIG. 39 , it could be confirmed that the catalyst structure according to above Example 4 exhibits electrochemical properties not inferior to conventional Pt catalysts used for hydrogen generation.

Although the invention has been described in detail with reference to exemplary embodiments, the scope of the present invention is not limited to a specific embodiment and should be interpreted by the attached claims. In addition, those skilled in the art should understand that many modifications and variations are possible without departing from the scope of the present invention.

INDUSTRIAL APPLICABILITY

According to an embodiment of the present invention, a catalyst structure and a method for preparing the same can be used as a catalyst for an oxygen evolution reaction (OER) or a hydrogen evolution reaction (HER).

SEQUENCE LIST PRETEXT

-   -   100: Catalyst structure     -   110: Base structure     -   120: Preliminary shell structure     -   130: Core structure     -   140: Shell structure 

1. A method for preparing an electrochemical catalyst, the method comprises: providing a base metal aqueous solution containing a base metal; hydrothermally synthesizing a base structure containing an oxide of the base metal by using the base metal aqueous solution; and by using a heat treatment method for the base structure in a sulfur (S)-containing reaction gas atmosphere, exchanging oxygen (O) on the surface of the base structure with the sulfur (S) of the reaction gas to form a catalyst structure which has a core structure containing the oxide of the base metal and a shell structure containing a sulfide of the base metal.
 2. The method of claim 1, wherein the reaction gas comprises hydrogen sulfide (H₂S), and the hydrogen sulfide is decomposed into sulfur (S) and hydrogen (H), in the forming of the catalyst structure, in which the decomposed sulfur (S) is adsorbed on the surface of the base structure, and the decomposed hydrogen (H) penetrates an inside of the base structure.
 3. The method of claim 2, wherein a plurality of pores are formed in the base structure as the decomposed hydrogen (H) penetrates inside of the base structure and reacts with the oxide of the base metal.
 4. The method of claim 3, wherein the base structure heat-treated in the reaction gas atmosphere comprises a first base metal oxide, and a second base metal oxide in which the first base metal oxide reacts with hydrogen (H) penetrated the inside of the base structure.
 5. The method of claim 1, wherein the shell structure comprises a first base metal sulfide in which the oxygen (O) on the surface of the base structure is exchanged with the sulfur (S) of the reaction gas, and a second base metal sulfide in which the first base metal sulfide is decomposed.
 6. The method of claim 1, the providing of the base metal aqueous solution comprises: preparing a source solution in which cobalt(II) nitrate hexahydrate is mixed with a solvent; and mixing the source solution with polyvinylpyrrolidone.
 7. An electrochemical catalyst comprising: a core structure including a first cobalt oxide, and a second cobalt oxide having a composition ratio different from a composition ratio of the first cobalt oxide; and a shell formed on a surface of the core structure and including a first cobalt sulfide, and a second cobalt sulfide having a composition ratio different from the composition ratio of the first cobalt sulfide, wherein a content of the first cobalt oxide, the second cobalt oxide, the first cobalt sulfide, and the second cobalt sulfide is controlled to improve oxygen generation efficiency in an oxygen evolution reaction (OER).
 8. The electrochemical catalyst of claim 7, wherein the first and second cobalt oxides comprise Co₃O₄ and CoO, respectively, and the first and second cobalt sulfides comprise Co₃O₄ and CoS, respectively.
 9. The electrochemical catalyst of claim 8, wherein the electrochemical catalyst comprises 49 wt % or more of the first cobalt oxide, 40 wt % or less of the second cobalt oxide, 11 wt % or less of the first cobalt sulfide, and 0.5 wt % or less of the second cobalt sulfide.
 10. The electrochemical catalyst of claim 7, wherein the core structure has a porous structure.
 11. The electrochemical catalyst of claim 10, wherein a diameter of pores formed in the core structure is 12 nm or less.
 12. An electrochemical catalyst comprising: a base structure in a form of a flat plate including a metal; a first material layer formed on a surface of the base structure and including an oxide of the metal; and a second material layer formed on the surface of the first material layer and including a sulfide of the metal.
 13. The electrochemical catalyst of claim 12, wherein the metal comprises any one of cobalt (Co), molybdenum (Mo), tungsten (W), or vanadium (V).
 14. The electrochemical catalyst of claim 12, wherein the electrochemical catalyst is used as a catalyst for an oxygen evolution reaction (OER) or a hydrogen evolution reaction (HER). 